Process for modifying textiles



United States Patent F 3,104,935 PROCESS FOR MODWYING TEXTHsES James Albert Moyse, Manchester, England, assignor to Imperial Chemical Industries Limited, London, England, a corporation of Great Britain No Drawing. Filed Apr. 14, 1960, Ser. No. 22,101 Claims priority, application Great Britain Apr. 20, 1959 4 Claims. (Cl. 8-1162) This invention relates to a process for modifying cellulosic textile materials.

It is already known from UK. patent specification 729,448 to treat textile materials with aqueous suspensions of colourless halogeno-l:3:5-triazines which are free of solubilising groups to confer resistance to micro-organisms.

We have now found that valuable modifications of cellulosic textile materials are obtained if these materials are treated with such suspensions in the presence of alkaline reacting substances and the materials are simultaneously or subsequently subjected to the action of heat.

Thus according to the present invention we provide a process for the modification of cellulosic textile materials which comprises contacting such materials in the presence of acid binding agents with an aqueous suspension of a substantially water-insoluble halogeno 1:3 triazine which is free from chromophon'c groups and from solubilising groups and simultaneously or subsequently subjecting the materials to the action of heat.

The term cellulosic materials as used herein includes the natural and regenerated forms of cellulose and also the secondary cellulose acetates. The term acid binding agents includes the oxides, hydroxides, carbonates and bicarbonates of the alkali metals and alkaline earth metals, the alkali metal salts of weak acids such as boric acid and also certain of the alkali metal phosphates.

The substantially water-insoluble triazines include those compounds in which alkyl, cycloalkyl, aralkyl or aryl groups are attached to a triazine ring, such as for example, 2-methyl-4 6-dichloro-1 :3 :S-tIiaZine and 2-phenyl-4z6-dichloro-1z3z5-triazine, or compounds in which an organic radical is attached to the triazine nucleus through a nitrogen, oxygen or sulphur atom, for example 2-anilino-4z6- dichloro 1:3 :5-triazine, 2:4-dianilino-6-chloro-l :3 :5-triazine, 2-fi-naphthoxy-4:6-dichloro-l:3 :S-triazine and 2-(pmethylphenylthio) -4 6-dichloro-l 3 S-triazine.

The triazines are employed in the form of aqueous dispersions or suspensions, which may be readily made by stirring or milling the triazine with a dispersing agent which may be anionic, cationic or non-ionic, for example, a long chain alkyl sulphate, a long chain quaternary ammonium salt or an alkylene oxide condensate of an alkylphenol.

The process of the invention may be performed by treating the cellulosic textile materials with an aqueous suspension or dispersion of the halogeno-lz3z5-triazine by (a) an exhaustion (absorption) technique, at a temperature up to the boiling point of the bath containing the aqueous dispersion of the halogeno-lz3s5-triazine, or (b) a padding operation (impregnation and squeezing) followed by drying or heating at an elevated temperature in the presence or absence of steam. The acid binding agent may be applied simultaneously with the triazine or from a separate bath, before or after the application of the triazine, if desired with an intermediate drying stage. The drying or heating atan elevated temperature may be carried out at temperatures up to 200 C.

In general it is found that useful modification of the properties of the cellulosic textile materials can be produced by application of from 0.1-10.0% by weight of the halogeno-lzBzS-triazines.

It is a further feature of the invention to incorporate with the textile material during the treatment process urea 3310-4335 Patented Sept. 24, 1963 or a water-soluble thiocyanate (e.g. potassium thiocyanate) or a Water-soluble sulphite (e.g. sodium sulphite) or .a quaternary ammonium salt (e.g. cetyl trimethylammonium bromide) to improve the degree of modification of the cellulose produced by the triazines. These substances may be applied to the textile material before, during or after treatment of the textile material with the water-insoluble triazine and the acid binding agent.

The properties which may be conferred on cellulosic textile materials as a result of modification according to the process of the invention include alternation in dyeing properties, handle, improvement in crease recovery properties, dimensional stabilisation, mouldproofing and waterrepellency.

This invention is illustrated but not limited by the following examples in which parts and percentages are by weight.

7 Example 1 Cotton wigan cloth is immersed in 92 parts of water containing 4 parts of sodium bicarbonate and 4 parts of finely dispersed 2-(2':4:5'-trichlorphenoxy) -4:6-dichloro- 1:3:5-triazine, previously dispersed in water bymilling for several hours with 20% of its weight of an ethylene oxide condensate of octylphenol. The fabric is squeezed until the weight of solution retained by the fabric is of the weight of dry fabric, and is dried at 50 C. The fabric is then heated for 2 minutes at 180 C., and finally Washed for 5 minutes at 60 C. in a solution containing 0.25% of an anionic detergent, rinsed in water and dried at 50 C.

The fabric so treated is found to be chemically modified as shown by its reduced solubility in cuprammonium hydroxide and in sulphuric acid compared with the untreated fabric, and by its modified dyeing properties, e.g. reduced uptake of the direct dyestuif Chlorazol Sky Blue PP. The rtreated fabric also resists wetting by water.

Example 2 A cotton poplin fabric is immersed in 92 parts of water containing 4 parts of sodium bicarbonate and 4 parts of finely dispersed 2-fl-naphthoxy-4:6-dichloro-l :3 :5 -triazine, previously dispersed in water by milling for several hours with 20% of its weight of cetyl trimethylammonium bro mide. The fabric is squeezed until the weight of solution retained by the fabric is 75% of the dry weight of fabric, and is dried at 50 C. The fabric is then heated for 2 minutes at 180 C. and finally washed for 5 minutes at 60 C. in a solution containing 0.25% of an anionic detergent, rinsed in water and dried at 50 C.

The pattern treated in this manner is found to possess modified dyeing properties. For example, the cloth becomes permanently stained on immersion in a solution of the diazonium salt, Brentamine Fast Black K Salt. The fabric is also found to possess reduced solubility in cuprammonium hydroxide compared with untreated material.

Example 3 Cotton wigan cloth is immersed in 83 parts of Water containing 3 parts of anhydrous sodium carbonate, 10 parts of urea and 4 parts of finely dispersed 1:2-bis-(4z6-dichloro-l:3:5-triazinylamino)ethane, previously dispersed by milling in water for several hours with 20% of its weight of an ethylene oxide condensate of octyl phenol. The fabric is squeezed until the Weight of solution retained by the fabric is 75 of the dry weight of the fabric, and is dried at 50 C. The fabric is then heated for 3 minutes at C. and finally Washed for 5 minutes at 60 C. in a solution containing 0.25% of an anionic detergent, rinsed in water and dried at 50 C.

The modified cotton fabric thus obtained shows a reduced uptake of the direct dyestutf Chlorazol Sky Blue FF compared with the untreated fabric. The fabric also J possesses reduced solubility in cuprammonium hydroxide. Example 4 then heated for minutes at 100 C. in the presence of steam, and finally Washed for 5 minutes at 60 C. in a solution containing 0.25% of an anionic detergent, rinsed in water and dried at 50 C.

The chemically modified viscose rayon fabric produced in this manner, shows a reduced uptake of the direct dyestufi Chlorazol Sky Blue FF, and a reduced solubility in cuprainmonium hydroxide, compared with untreated fabric.

Example 5 Cotton limbric is immersed in 94 parts of Water containing 4 parts of sodium bicarbonate and 2 parts of finely dispersed 2:4-diphenoxy-6-ch1oro-1 :3 :S-triazine, previously dispersed in water by milling for several hours with 20% of its weight of an ethylene oxide condensate of octylphenol. After squeezing the fabric until the weight of solution it retains is 75% of its dry weight the fabric is dried at 50 C. and then heated at 180 C. for 2 minutes. It is finally washed for 5 minutes at 60 C. in a solution containing 0.25% of an anionic detergent, rinsed in water and dried at 50 C.

The fabric treated in this manner is found to possess modified dyeing properties, showing, for example, a reduced uptake of the direct dyestuif, Chlorazol Sky Blue FF, compared with the untreated fabric.

Example 6 A viscose rayon staple fibre fabric is immersed in 86 parts of water containing 3 parts of sodium bicarbonate, 8 parts of urea and 3 parts of finely dispersed 2-p-octadecylanilino-4 6-dichloro-1 3 :5 -triazine, previously dispersed in water by milling for several hours with 20% of its weight of an ethylene oxide condensate of octylphenol. The fabric is squeezed until the weight of solution retained by the fabric is 90% of the dry weight of the fabric and is dried at 50 C. It is then heated at 180 C. for 2 minutes and finally washed for 5 minutes at 60 C. in a solution containing 0.25% of an anionic detergent, rinsed in water and dried at 5 0 C.

The chemically modified viscose rayon fabric thus pro- 7 duced shows a reduced uptake of the direct dyestulf,

Chlorazol Sky Blue FF, compared with the untreated fabric and becomes permanently stained when immersed in a solution of the diazonium salt, Brentamine Fast Black K Salt. The treated fabric also resists wetting by water.

What I claim is:

1. Process for modification of cellulose textile materials which consists essentially in impregnating said textile materials in the presence of .an acid-binding agent with an aqueous suspension of a substantially water-insoluble halogeno-1z3z5-triazine, which is free from chromophoric groups and from solubilising groups, and selected from the class consisting of -alkyl-, cycloalkyl-, and .aralkyl-, and

aryl-substituted monoand di-halogeno triazine rings, and 7 said tn'azine rings in which the organic radical is attached to the triazine nucleus through an atom selected from the group consisting of nitrogen, oxygen, and sulfur .atoms and subjecting the [treated textile materials to the action of heat up to about 200 C.

2. The process according to claim 1, wherein said treated textile materials are subjected to the action of heat simultaneously with the contacting thereof with said aqueous suspension.

3. The process according to claim 1, wherein said treated textile materials are subjected to the action of heat subsequent to the contacting thereof with said aqueous suspension.

4. Modification of the process according to claim 1 wherein the textile material is also treated with a substance selected from the group consisting of urea, watersoluble thiocyanates, Water-soluble sulphites and quaternary ammonium salts in conjunction with treatment of the textile material with the Water-insoluble triazine and acid binding agent.

References Cited in the file of this patent UNITED STATES PATENTS 2,680,057 lanes Jan. 1, 1954 2,786,734 Evans et a1 Mar. 26, 1957 2,892,674 Sause et a1 June 30, 1959 2,971,815 Bullock et al Feb. 14, 1961 FOREIGN PATENTS 729,448 Great Britain May 4, 1955 

1. PROCESS FOR MODIFICATION OF CELLULOSE TEXTILE MATERIALS WHICH CONSISTS ESSENTIALLY IN IMPREGNATING SAID TEXTILE MATERIALS IN THE PRESENCE OF AN ACID-BINDING AGENT WITH AN AQUEOUS SUSPENSION OF A SUBSTANTIALLY WATER-INSOLUBLE HALOGENO-1:3:5-TRIAZINE, WHICH IS FREE FROM CHROMOPHORIC GROUPS AND FROM SOLUBILISING GROUPS, AND SELECTED FROM THE CLASS CONSISTING OF ALKYL,- CYCLOALKYL-, AND ARALKYL-, AND ARYL-SUBSTITUTED MONO- AND DI-HALOGENO TRIAZINE RINGS, AND SAID TRIAZINE RINGS IN WHICH THE ORGANIC RADICAL IS ATTACHED TO THE TRIAZINE NUCLEUS THROUGH AN ATOM SELECTED FROM THE GROUP CONSISTING OF NITROGEN, OXYGEN, AND SULFUR ATOMS AND SUBJECTING THE TREATED TEXTILE MATERIALS TO THE ACTION OF HEAT UP TO ABOUT 200*C. 